Process for rapid solution of vinyl resins



115:imordermto iacilitate handlingmrinmanycases .tlon provides a'greater dissolving power than towemployLthea-material at all. Ingsecuring the the pure solvent, many combinations which have ldesired:solution:orrdispersion,litiscustomaryto a lowerultimate dissolvinsypowerthan that 01' zassiststhee:combination-lof the materials by-emthepure solvent also exhibit this remarkable in- ,i ployinga-suoh aids asnheat;pressure,mechanical. creasein rate ofsolution (or dispersion). There- "mwworking randzcombinationsof these, buteven so Ioreit is believed that this increase is due large-L Mlle-processionsolutionwor dispersion, is often ly to the greater penetrating power of the mixverysslowvandllaborious ture. It may be. that prevention of agglomera- .-:'I his1;invention-is lconcerned with theaiormation of resin particles by the penetrant compo- :Ollwflflflbllltlbhfi; undisperslons; or. suchartiflnentof the mixture is a strong factor in accomcialtiresins:as thevinyl resins,andthe*principal plishing therapid dispersion, but it is not the object on-theiinventionais to provideaneiiicient only-one, for single large piecesof the resin dis- =process"rwhereby solvents capable of dissolving solve, or disperse, much more rapidly in the y(or dispersingl dame-quantitiesoftheresins may .xsolvent-penetrant mixture than in thepure sol.-

lbeasmade -to*idowso; atvany'idesired rate up toone vent. However, it is, to be understood that the 40!iarwgreater-"rapidity than {those heretoiore invention is notto be limited by any theoretical lspossible. f explanationsor discussion advanced herein.

"The-vinyl'rresinsf-to (which this invention is In order to secure the most rapid acting mixparticularlyapplicablevare those whichare, in ture, itis necessary to limit the proportion of' egeneral, soluble in ketones, and: insoluble 11h penetrant to solvent to sucha concentration that fl ethers, 'i-hydrocarbona i'acids uandlalkalis, and thewultimate dissolving power'of the mixture is 5 ,rewaterr .-'I'-hey-,:,are=solublevto some extent in cer- "not unduly less than that of the pure solvent. tainwaliphatieesters. Resins -such ;as these may -.=0therwise the rapid dispersing action of the mixmbemnade;iorfiexample; byzthe conjoint poiymeri ture will be largely counteracted by its low ulwzation -sot'vaavinyl 'halideiwitha vinyl ester oi' ia timate dissolving power. tloweraliphatictacidiiarewsuitable,andtheonesto To illustrate the remarkable effectiveness of .which iithisainvention iis cbestxadaptedare those this invention, thefollowing examples are given. not thisitypel inwhichrtheaproportion of vinyl For comparative purposes in the examples, the "halide i-preseiritzrin (the "polymerized product is temperature in each case was held at about 25 irom i'lil%atol195.% by= weight andwhich have an 0., and rolling agitation was used with a con- 36 averageinacromolecular weight 01 about 10,000, stant speed 01 170R. P. M. The resin used was :orwmore. *lMoleculanweightsreierred to'herea conjoint polymer of vinyl chloride with vinyl in arexthosecalculatedbymeansof Staudingers acetate, containing 85% to 90% by weight of .iormula' troniaviscosity determinations on soluvinyl chloride, and having an average macromotlonsw-ot.the materials.) Specifically, thezconlecular weight of about 10,000.

40 joint polymers (or ivinyl-chloridevwith vinylace- W I 40 -tate,:propionate.=or butyratearepreferred. l l

.i l= 1 v n y b attained 'Ihreesamples of. powdered resin 0! 12 grams ibywcontactingetheanresinwith asolventwhilethe 'each sized to p ass through a 20 mesh screen resin-launderathewaction gofailiquidrenetrantl (openings 0.86 mm.), were dissolved as follows:

The.penetrant mayl itselfiexert'fa':solventgactlon Th a swer m lv i 100 of acetone 45 D h es itimay b ya non-solvent, but (solvent); the second was dissolved in 85 cc. ace- -it -mustwbe lflt-ileashpfll'tlillymiscible with t toneaiter being thoroughly wetted with 15 cc.

sblven e p oyed. This treatment can m of the penetrant, carbon tetrachloride (nonsolrreadily be accomplished' by mix ns th penetrant vent); and the third was dissolved in 65. cc. acewithsthe-=solvent prior 'to contact with the resin. tone after beingwetted with 35 cocarbon tetr'a- 50 onif the res n i pfl f rflneesranules. chloride. Complete solution of the samples was "by mer lytwet ins l p CtI-flht eflected in 145 minutes, 30 minutes, and 5 mintp'rlbfrto l contact with .theisolvent. utes, respectively.

. X F'I'heimaximumlconcentration oi "airesin which EXAMPLE n lid-Ia solvent'will.hold 'withoutforming a gel may be r =termed-zthezultimate dissolving power oi 'the Two. samples of powdered resin of '12 grams solvent for that resin. For 5a particular resin, each, prepared as in Example I, were dissolved theultimateaidissolving power. of. mixtures of solas follows: The first was dissolved in cc. aceflyentszandzpenetrantsmay be greater or less than tone-after being treated with 15 cc. carbon bisulflde (nonsolvent); and the second was dissolved no iflatenterl Apriiiso,"-1940 V l 5"PROGEBB FIOBTEAPIDiSOLUTION0F i 5 a vmmassms l .Yometoa mismuh;waiver, .oilio, timer to Garbide-and; Carbon! Chemicals Gorporatiom awcorporation ofsNewi-York 1 y ins iration November same, v

1;SerlaldNo. 108,497

some". 101130-82),

In the.proddctionbniztilitationof plastic com- -positionsrcontaining suchfmaterials as artificial rresins ituislzoiten necessary to *dissolve,.or disvperse; thesewmaterials' in some suitable solvent to that wot ithepure solvent depending upon: the

'coinbination- -oisolvent and penetrant employed. iAlthoughutheri-emarkable increasein rate of so- --lution (or dispersion) may be enhanced in those cases where the solvent I and penetrant combina- 45 cc. acetone after treatment with 55 cc. carbon bisulfide. Complete solution of the samples was effected in 19 minutes and 1%, minutes,

respectively. I

EXAMPLE III I Two samples of powdered resin of 1.2 grams each, prepared as in Example I, were dissolved as follows: The first was dissolved in 90 cc. acetone after being thoroughly wetted with 10 cc. isopropyl ether; and the second was dissolved in 75 cc. acetone after being thoroughly mixed with cc. isopropyl ether. Complete solution of the samples was eflfected in 53 minutesand 9 minutes, respectively.

ExAMPLr: IV

170 R. P. M. was employed. In table A theresin was dissolved in a single solvent, and tables 3 and C apply to previously made mixtures of penetran't and solvent.

I Table A (no penetrant) I Time required Solvent for complete solution Minutes cc. propylene oxide 65 100 cc. met yl ethyl keto e-. 100 cc. mesityl oxide 182 100 cc. acetone 240 100 cc. methyl isobutyl ketone" 542 100 cc. dipropyl ketone 100 3e flinxnn 100 cc. ethyl acetate 2800 Table B (penetrant as a nonsolvent) Time required Solvent Penetrant for comlate so ution Minutes 55 cc. acetone 45 cc. carbon bisulflde 57 80 cc. propylene oxide 20 cc. carbon blsulflde"... 58 65 cc. methyl ethyl ketone- 35 cc. carbon .msulllde. 80 70 cc. esityl oxide 30 cc. carbon bisulflde. 123 75 cc. acetone 26 cc. carbon tetrachloride. 80 cc. methyl isobutyl keton 20 cc. carbon bisulflde 90 cc. dioxan 10 cc. carbon bisulilde 490 90 cc. ethyl acetate 10 cc. carbon bisulfirle.-... v 400 Table C (pure penetrant ewhzbzts a solvent actzon) Time I required Solvent Penetrant for complete solution Minutes 70 cc. acetone 30 cc. toluene 119 75 cc. acetone. 25 cc. dioxan. 120 750:. acetone- 25 cc. monochlorbenzcne 134 75 cc. acetone. 25 cc. d1propylketone. 154 80 cc. acetone 20 cc. trichlorethylene 158 75 cc. acetone 25 cc. methyl isobutyl 183 ketone. 95 cc. acetone 5 cc. ethyl acetate... 218

It will be noted that, in the above examples, the procedure for securing rapid solution of the powdered resin was to treat the resin with the penetrant prior to contact with the solvent; whereas rapid solution of the'resin rods was secured by treatment with a previously made mixture of the solvent and penetrant. However, a solution rate far greater than that of. the pure solvent is obtained regardless of whether-the resin is given a prior treatment with the penetrant. or is dissolved in a previously made mixture of the penetrant and solvent. In the case of the powdered resin,

treatment with the penetrant prior to contact with the solvent gave more rapid solution of the resin than was obtained with a previously made mixture having the same proportions, provided difference whether the resin is treated with the A penetrant prior to, or in admixture with the sol vent.

Many'other experiments have been carried out which have demonstrated effectively the general utility. of the process of this invention. Earamples of suitable mixtures of solvent and penetrant liquidswhich have been used in carrying out the invention according to the procedure illustrated above, and in addition to the examples given, include dipropyl ketone with carbon bisulfide, ethylene dichloride with carbon bisulfide, and mesityl oxide with acetone. In every case, the

process resulted in a remarkable increase in the rate of solution or dispersion of .the resin that was impossible of attainment by other known means.

Various modifications of the process will suggest'themselves to those skilled in the art, and

such variations are included within the scope of this. invention as defined by the appended claims.

I claim:

1. Process for rapidly forming dispersions or wetted resin with a solvent selected from the,

group consisting of acetone, methyl ethyl ketone.

dipropyl ketone, mesityl oxide, propylene oxide,

' methyl isobutyl ketone, ethyl acetate, dioxan and ethylene dichloride to effect solution of said resin at a faster rate than is obtainable by likeuse of.

any of the solvents singly,-said solvent being at least partially miscible with said penetrant.

2. Process for rapidly forming dispersions or" solutions of vinyl resins substantially identical with'resins resulting from the conjoint polymerization of a'vinyl halide with a vinyl ester of a. lower aliphatic acid, which comprises wetting said resin with a nonsolvent penetrant selected from the group consisting of carbon bisulfide,

carbon tetrachloride, and isopropyl ether and thereafter agitating the wetted resin with a solvent for the resin to efi'ect' solution thereof at a faster rate than is obtainable by like use ofthe' solvent singly, said solvent being at least 3. Process for rapidly forming dispersions or solutions of vinyl resins substantially identical with resins resulting from the conjoint polymerization of vinyl chloride with vinyl acetate, said resins containing from 70% to 95% vinyl chloride in the polymer, which comprises wetting said resins with from about 10 to about 55 parts of a nonsolvent selected from the group consisting of carbon bisulfide, carbon tetrachloride and isopropyl ether, and thereafter agitating the wetted resins with from about 90 to about 45 parts of acetone to effect solution thereof at a rate at least twice as fast as is obtainable by like use of acetone singly.

CARLETON N. SM ITH. 

